Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies

• Published in: The journal of physical chemistry letters 2018-05, Vol.9 (9), p.2164-2169
• Main Authors: Ma, Ying-Zhong, Lin, Haoran, Du, Mao-Hua, Doughty, Benjamin, Ma, Biwu
• Format: Article
• Language: English
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.8b00761

Excitons in low-dimensional organic–inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton–phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C6H13N4)3Pb2Br7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton–exciton annihilation process, a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. We further identify a fast and dominant PL decay component with a lifetime of ∼2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.